JP2014091753A - Non-halogen flame retardant resin composition and electric wire/cable using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-halogen flame-retardant resin composition excellent in mechanical properties such as tensile strength and elongation, flame retardancy, flexibility and water resistance and to provide an electric wire/cable using the resin composition.SOLUTION: There is provided a non-halogen flame-retardant resin composition which is constituted of: 100 pts.mass of a polymer in total comprising 10 to 30 pts.mass of polypropylene, 4 to 10 pts.mass of a ternary polymer of ethylene, an α-olefin having a polar group and maleic anhydride, and 54 to 86 pts.mass of a polyolefin-based resin; and 180 to 250 pts.mass of a non-halogen-based flame retardant.

Description

  The present invention relates to a halogen-free flame retardant resin composition and an electric wire / cable using the same.

  As a flame retardant resin composition not containing a halogen compound, a composition obtained by adding a metal hydroxide such as magnesium hydroxide or aluminum hydroxide to a polyolefin resin is used. These compositions do not generate toxic gases such as hydrogen chloride and dioxins during combustion, so they can prevent the generation of toxic gases during fires and secondary disasters, and are incinerated when discarded. There is no problem even if you do. However, compared to conventional halogen flame retardants, the flame retardant effect due to the addition of metal hydroxide is small and the desired flame retardancy is often not obtained, so the amount of metal hydroxide added is increased. To be done.

  The increase in the amount of the metal hydroxide added as described above has a problem that the mechanical characteristics are remarkably lowered accordingly. For example, mechanical properties such as tensile strength and elongation are extremely reduced with the addition of metal hydroxide. Therefore, it is common to employ polypropylene (hereinafter, may be abbreviated as PP) which is a high-strength polymer having high crystallinity for the polymer itself. However, since PP cannot contain a large amount of a filler such as a metal hydroxide, an elastomer having low crystallinity such as EVA is added, and this elastomer is made to contain a filler.

  However, since PP and elastomer are generally incompatible with each other, even if they are simply blended, they are not mixed uniformly and often do not exhibit good characteristics. Therefore, a third polymer is added for the purpose of compatibilizing both polymers. As such a third polymer, a nonpolar polymer modified with a polar group such as an acid is generally used. Specifically, an ethylene copolymer modified with maleic anhydride is used. The used composition is disclosed (for example, refer patent document 1).

JP 2009-19190 A

  However, in the researches of the present inventors, when the modified polymer as described above is used as the third polymer, it is difficult to increase the amount of polar groups introduced. A sufficient amount cannot be obtained. Therefore, it was found that the compatibility between PP and elastomer was insufficient, and an extreme decrease in volume resistivity during immersion was observed. In addition, when the amount of the modified polymer added is increased, the ratio of PP and elastomer in the polymer is reduced, so that the excellent tensile strength and elongation of PP, and the flexibility and filler acceptability of elastomer are decreased. Will end up.

  Accordingly, the present invention provides a non-halogen flame retardant resin composition excellent in mechanical properties such as tensile strength and elongation, flame retardancy, flexibility, and water resistance, and an electric wire / cable using the same. With the goal.

  As a result of diligent research conducted by the present inventors to achieve the above-described object, a terpolymer of ethylene, an α-olefin having a polar group, and maleic anhydride is used as a compatibilizing agent for polypropylene and polyolefin resin. It was considered that the amount of maleic acid in the polymer can be increased because maleic acid can be used as one of raw materials for polymer synthesis instead of modification. Thereby, the compatibility between polymers is improved, and it is found that a non-halogen flame retardant resin composition excellent in mechanical properties such as tensile strength and elongation, flame retardancy, flexibility, and water resistance can be obtained. The present invention has been completed. That is, according to the present invention, the following non-halogen flame retardant resin composition and electric wires / cables using the same are provided.

[1] 10 to 30 parts by mass of polypropylene; 4 to 10 parts by mass of terpolymer of ethylene, α-olefin having a polar group and maleic anhydride; and 54 to 86 parts by mass of polyolefin resin other than polypropylene A non-halogen flame retardant resin composition comprising a polymer comprising 100 parts by mass and 180 to 250 parts by mass of a non-halogen flame retardant.
[2] The type D durometer hardness is 50 to 60, and the volume resistivity after being immersed in hot water at 80 ° C. for 30 days is 1.0 × 10 10 Ω · cm or more. Non-halogen flame retardant resin composition.
[3] The non-halogen flame retardant resin composition according to [1] or [2], wherein the polyolefin-based resin is an ethylene / vinyl acetate copolymer having a vinyl acetate content (VA amount) of 20 to 45%. .
[4] The non-halogen flame retardant resin composition according to any one of [1] to [3], wherein the terpolymer is a terpolymer of ethylene, ethyl acrylate, and maleic anhydride.

[5] An electric wire comprising a conductor and an insulator coated and formed on the outer periphery of the conductor using the non-halogen flame-retardant resin composition according to any one of [1] to [4].

[6] A conductor and an insulator formed on the outer periphery of the conductor, each of which includes a conductor and a plurality of wires that are twisted together, and a pressing member wound around the periphery of the wires that are twisted together, A cable comprising: a sheath formed by coating the outer periphery of the pressing member with the non-halogen flame-retardant resin composition according to any one of claims 1 to 4;

  According to the present invention, there are provided a halogen-free flame retardant resin composition excellent in mechanical properties such as tensile strength and elongation, flame retardancy, flexibility, and water resistance, and an electric wire / cable using the same. .

A cable according to an embodiment of the present invention (a cable in which a copper conductor and an insulator coated and formed on the outer periphery thereof are provided, and the outer periphery of a plurality of twisted electric wires are covered with a press-wound tape and a sheath. Is a cross-sectional view schematically showing. It is sectional drawing which shows typically the electric wire (electric wire provided with the copper conductor and the insulator coat | covered and formed in the outer periphery) which concerns on embodiment of this invention.

[Summary of embodiment]
The non-halogen flame retardant resin composition according to the present embodiment is a non-halogen flame retardant resin composition containing a polymer containing a polyolefin resin and polypropylene, and a non-halogen flame retardant. A polymer consisting of 100 parts by mass in total, including 4 to 10 parts by mass of a terpolymer of α-olefin having a polar group and maleic anhydride; and 54 to 86 parts by mass of a polyolefin-based resin other than polypropylene; It contains 180 to 250 parts by mass of a flame retardant.

[Embodiment]
Hereinafter, the non-halogen flame retardant resin composition of the present embodiment and the electric wires and cables using the non-halogen flame retardant resin composition as an insulator or sheath will be described.

I. Non-halogen flame-retardant resin composition The non-halogen flame-retardant resin composition of the present embodiment comprises 10 to 30 parts by mass of polypropylene; 4 to 10 parts by mass of terpolymer of ethylene, α-olefin having a polar group and maleic anhydride And a polymer composed of a total of 100 parts by mass including 54 to 86 parts by mass of a polyolefin resin and 180 to 250 parts by mass of a non-halogen flame retardant. Hereinafter, it demonstrates concretely for every component.

1. Polymer As described above, the polymer used in the present embodiment is configured to include polypropylene; a terpolymer of ethylene, an α-olefin having a polar group and maleic anhydride; and a polyolefin resin.

(polypropylene)
(PP) constituting the polymer is generally roughly classified into homo PP (propylene homopolymer), random PP, and block PP.

  Examples of the random PP include an ethylene / propylene random copolymer and an α-olefin / propylene random copolymer. Examples of the block PP include an ethylene / propylene block copolymer and an α-olefin / propylene copolymer. The block PP also includes those in which the polypropylene chain and the ethylene-propylene copolymer chain are not chemically bonded. Although there is no restriction | limiting in particular as PP used for this Embodiment, Block PP is preferable. These may be used alone or in combination of two or more as long as they are within the specified range.

  The addition amount of a polypropylene is 10-30 mass parts. When the amount is less than 10 parts by mass, sufficient tensile strength cannot be obtained. When the amount exceeds 30 parts by mass, the elongation decreases and the hardness becomes hard, and the wire cannot be applied as an electric cable.

(Polyolefin resin)
Examples of the polyolefin resin constituting the polymer include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), linear very low density polyethylene (VLDPE), high density polyethylene (HDPE), and ethylene-acrylic. Ethyl acid copolymer (EEA), ethylene vinyl acetate copolymer (EVA), ethylene-glycidyl methacrylate copolymer, ethylene-butene-1 copolymer, ethylene-butene-hexene terpolymer, ethylene-propylene -Diene terpolymer (EPDM), ethylene-octene copolymer (EOR), poly-4-methyl-pentene-1, hydrogenated styrene-butadiene copolymer (H-SBR), ethylene and carbon number Examples include copolymers with 4 to 20 α-olefins, ethylene-styrene copolymers, and the like. Bets can be, they can be blended alone, or two or more as long as it is within the specified range.

  Although there is no restriction | limiting in particular as polyolefin resin, EVA is preferable and EVA with a vinyl acetate content (VA amount) of 20-45 mass% is further more preferable.

  The addition amount of the polyolefin resin is 54 to 86 parts by mass. When the amount is less than 54 parts by mass, the amount of PP added in the polymer is excessively increased, resulting in a decrease in elongation characteristics. When the amount exceeds 86 parts by mass, the tensile strength of PP in the polymer is decreased.

(Ternary copolymer)
There is no particular limitation on the terpolymer of ethylene, α-olefin having a polar group, and maleic anhydride constituting the polymer. Examples of the α-olefin having a polar group include olefins having a polar group such as an acryloyl group and an acyl group, and more specifically, ethyl acrylate, methyl acrylate, butyl acrylate, and vinyl acetate. Can do. Moreover, as a suitable example of a ternary copolymer, ethylene, ethyl acrylate, and maleic anhydride can be mentioned.

  The addition amount of the ternary copolymer is 4 to 10 parts by mass. When the amount is less than 4 parts by mass, the compatibility between PP and the polyolefin resin is insufficient, and the water resistance decreases. When the amount exceeds 10 parts by mass, the elongation characteristics are deteriorated.

2. Non-halogen flame retardant As the non-halogen flame retardant used in the present embodiment, for example, metal hydroxide such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide; melamine, cyanuric acid, isocyanuric acid, melamine cyanurate, 1,3,5-triazine derivatives such as melamine sulfate; zinc compounds such as zinc stannate, zinc hydroxystannate, zinc borate and zinc oxide; boric acid compounds such as calcium borate, barium borate and barium metaborate; Phosphorus flame retardants: Intumescent flame retardants composed of a mixture of components that foam and solidify during combustion. These can be used alone or in a blend of two or more.

  These flame retardants may be silane coupling agents, titanate coupling agents, fatty acids such as stearic acid or calcium stearate or fatty acid metal salts, and the like.

  The addition amount of the non-halogen flame retardant resin composition is 180 to 250 parts by mass. When the amount is less than 180 parts by mass, sufficient flame retardancy cannot be obtained, and when the amount exceeds 250 parts by mass, the elongation characteristics are remarkably deteriorated.

3. Other additives The halogen-free flame retardant resin composition of the present embodiment includes, in addition to the polymer and the halogen-free flame retardant, an antioxidant, a metal deactivator, a crosslinking agent, a crosslinking aid, as necessary. Additives such as agents, lubricants, inorganic fillers, compatibilizers, stabilizers, carbon black, and colorants can be blended. Furthermore, it may be crosslinked with an organic peroxide or with radiation such as an electron beam.

  Although there is no restriction | limiting in particular as antioxidant, For example, a phenolic antioxidant, a sulfur type antioxidant, an amine type, a phosphorus type antioxidant, etc. can be mentioned. Although there is no restriction | limiting in particular as a phenolic antioxidant, For example, dibutylhydroxytoluene (BHT), pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3 , 5-tris (3,5-di-t-butyl-4-hydroxy-benzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, thiodiethylenebis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like, and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is preferable.

  Although there is no restriction | limiting in particular as a sulfur type antioxidant, For example, didodecyl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, tetrakis [Methylene-3- (dodecylthio) propionate] methane can be mentioned, and tetrakis [methylene-3- (dodecylthio) propionate] methane is preferable.

  The amine antioxidant is not particularly limited, and examples thereof include 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, phenyl-1-naphthylene, alkylated diphenylamine, octylated diphenylamine, 4, 4′-bis (α, α-dimethylbenzyl) diphenylamine, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, p- (p-toluenesulfonylamido) diphenylamine, N, N′-di-2 -Naphtyl-p-phenyldiamine, N, N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N '-(1,3-dimethylbutyl)- p-phenylenediamine, N-phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl)- p-phenylenediamine, 1,3-benzenedicarboxylic acid bis [2- (1-oxo-2-phenoxypropyl) hydrazide, 2 ′, 3-bis [[3- [3,5-di-tert-butyl-4 -Hydroxyphenyl] propionyl]] propionohydrazide, 3- (N-salicyloylamino) -1H-1,2,4-triazole, dodecanedioic acid bis [N2- (2-hydroxybenzoyl) hydrazide] and the like. be able to.

  These antioxidants can be used alone or in combination of two or more.

  The metal deactivator has the effect of stabilizing metal ions by chelate formation and suppressing oxidative degradation, and the structure thereof is not particularly limited, but N- (2H-1,2,4-triazol-5-yl) Salicylamide, dodecanedioic acid bis [N2- (2-hydroxybenzoyl) hydrazide], 2 ', 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propiono Examples thereof include hydrazide, and 2 ′, 3-bis [[3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide is preferable.

  The crosslinking aid is not particularly limited, and examples thereof include trimethylolpropane trimethacrylate (TMPT) and triallyl isocyanurate (TAIC).

  Although there is no restriction | limiting in particular as a lubricant, For example, a fatty acid, a fatty acid metal salt, a fatty acid amide etc. can be mentioned, Specifically, a zinc stearate can be mentioned. These can be used alone or in combination of two or more.

  The inorganic filler is not particularly limited, and examples thereof include clay, talc, and silica. These can be surface-treated with a surface treatment agent such as fatty acid or silane. These can be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular as carbon black, For example, carbon black for rubber | gum (N900-N100: ASTM D 1765-01) can be mentioned.

  Although there is no restriction | limiting in particular as a coloring agent, For example, the color masterbatch for non-halogen etc. can be mentioned.

The halogen-free flame retardant resin composition of the present embodiment has a hardness of 50 to 60 as type D durometer hardness and is immersed in warm water at 80 ° C. for 30 days from the viewpoint of flexibility and water resistance. The subsequent volume resistivity is preferably 1.0 × 10 ¹⁰ Ω · cm or more.

II. 2. Electric wire As shown in FIG. 2, the electric wire of the present embodiment includes a copper conductor 1 and an insulator 2 coated and formed on the outer periphery of the copper conductor 1 using the above-described non-halogen flame-retardant resin composition, It is configured with.

III. Cable As shown in FIG. 1, the cable according to the present embodiment includes a copper conductor 1 and an insulator 2 that is coated and formed on the outer periphery of the copper conductor 1, and a plurality of twisted electric wires and a twisted wire. The above-mentioned non-halogen flame retardant resin composition is applied to the outer periphery of a plurality of combined electric wires, for example, a pressing member wound together with the paper interposition 4, for example, the pressing and winding tape 5 and the outer periphery of the pressing and winding tape 5. And a sheath 3 that is covered and formed by using. In this case, the insulator 2 is preferably manufactured using the above-described non-halogen flame retardant resin composition.

  Hereinafter, the non-halogen flame retardant resin composition and the electric wire / cable of the present invention will be described more specifically with reference to examples. Note that the present invention is not limited in any way by the following examples.

Example 1
PP (manufactured by Nippon Polyethylene Co., Ltd., trade name: BC8A) 10 parts by mass, EVA (vinyl acetate content (VA amount): 25% by mass, MFR: 2.0) 84 parts by mass, ethylene-ethyl acrylate-maleic anhydride 6 parts by mass of a copolymer (trade name: Bondine LX4110, manufactured by Arkema Co., Ltd.), magnesium hydroxide (trade name: Magseeds S6, manufactured by Kamishima Chemical Co., Ltd.), hindered phenol antioxidant (trade name: manufactured by BASF Japan) Irganox 1010) 1.0 part by mass and 0.5 part by mass of a sulfur-based antioxidant (trade name: AO-412S, manufactured by ADEKA) were blended, and the starting temperature was 40 ° C. and the end temperature was 190 ° C. by a pressure kneader. After kneading, the kneaded product (non-halogen flame retardant resin composition) was pelletized.

  As shown in FIG. 2, the kneaded product by the above-mentioned pressure kneader is used as the insulator 2 on the outer periphery of the copper conductor 1, so that the outer diameter of the wire is 0.98 mm and the insulator thickness is 0.25 mm. Thus, it extrude | pushed out by setting temperature 200 degreeC.

  As shown in FIG. 1, the cable is produced by twisting three of the above-mentioned electric wires together with paper intervening 4, applying press-wound tape 5 thereon, and kneaded with the above-mentioned pressure kneader on the outer periphery thereof. Was extruded and coated as a sheath 3.

  The compounding components of the non-halogen flame retardant resin composition used in Example 1 are shown in Table 1, and the results of the evaluation of the electric wires described later are shown in Table 1.

(Examples 2 to 13)
The same procedure as in Example 1 was conducted except that the components of the halogen-free flame retardant resin composition were changed to those shown in Table 1. Table 1 shows the results of the evaluation of the electric wires.

(Comparative Examples 1-10)
The same procedure as in Example 1 was conducted except that the halogen-free flame retardant resin composition blending components were changed to those shown in Table 2. Table 2 shows the results of the electric wire evaluation.

(Evaluation method of electric wire)
The evaluation of the electric wire was determined by the following method.

(1) Tensile test The produced electric wire was subjected to a tensile test in accordance with JIS C 3005. As for the elongation, less than 150% was evaluated as x (failed), 150-300% was evaluated as ◯ (accepted), and more than that was evaluated as ◎ (accepted with tolerance). Tensile strengths of less than 10 MPa were evaluated as x (failed), 10-13 MPa were evaluated as ◯ (accepted), and more than ◎ (accepted with tolerance).

(2) Flame Retardancy Test A vertical combustion test (VW-1) in the shape of an electric wire was performed. Judgment was made with ◎ (pass with tolerance) for combustion time less than 30 seconds, ○ (pass) for more than 30 seconds and less than 1 minute, and X (fail) for more than 1 minute.

(3) Hardness test A hardness test was performed on a sheet-shaped sample in accordance with JIS K 6253. Measurements were made using a type D durometer, and those having a value of 60 or less were evaluated as ◯ (passed) and those having a value larger than 60 were evaluated as x (failed).

(4) Volume resistivity The produced 1 mm sheet was immersed in warm water at 80 ° C for 30 days, and then the volume resistivity was measured. The volume resistivity was measured according to JIS K 6271. 1 × 10 ¹³ Ω · cm or more ◎ (pass with tolerance), 1 × 10 ¹⁰ Ω · cm or more, less than 1 × 10 ¹³ Ω · cm ○ (pass), 1 × 10 ¹⁰ Those less than Ω · cm were evaluated as x (failed).

  As shown in Table 1, in Examples 1 to 13, all the properties of the tensile test, flame retardancy test, hardness test, and water resistance test in the table are good results. In Examples 1 and 2, the addition amount of PP was changed, but when PP is small, the tensile strength tends to decrease and the elongation tends to improve. . In Examples 3 to 4, the amount of addition of the terpolymer of ethylene, the α-olefin having a polar group, and maleic anhydride was changed, but when the addition amount is small, the water resistance is slightly lowered and the addition amount is large. Although the elongation characteristics tend to be reduced, the characteristics were good at the specified 4 to 10 parts by mass. The polyolefin resin was changed in Examples 3 and 5 to 8, and all of them had good characteristics. In addition, Examples 3 and 5 using EVA having a VA amount of 20 to 45% by mass as the polyolefin-based resin are improved in flame retardancy compared to Examples 6 to 8 using other polymers. From the viewpoint of improving the flame retardancy, it is preferable to use EVA having a VA amount of 20 to 45% by mass. In Examples 9-10, although the addition amount of the non-halogen flame retardant was changed, the flame retardancy tends to improve with the increase in the addition amount, and good characteristics were obtained at the specified 180-250 parts by mass. In Example 11, melamine cyanurate was added as a non-halogen flame retardant, but the flame retardancy was improved as compared with Example 6 without addition, and the addition is preferable from the viewpoint of flame retardancy. In Example 12, a lubricant, an inorganic filler, and a colorant were added. In Example 13, a lubricant, an inorganic filler, and carbon black were added, but the characteristics were good.

  On the other hand, as shown in Table 2, Comparative Example 1 in which the amount of PP added was less than specified was insufficient in tensile strength. Further, Comparative Example 2 in which the amount of PP added was larger than the specified amount had insufficient elongation characteristics. In Comparative Example 3 in which the addition amount of the terpolymer of ethylene, α-olefin having a polar group, and maleic anhydride is less than the specified amount, the water resistance is insufficient, and in Comparative Example 4 in which the addition amount is higher than the specified value, the elongation characteristics are not good. It was enough. In Comparative Examples 5 to 6 using maleic acid-modified PP as a third polymer and Comparative Examples 7 to 8 using maleic acid-modified PE, water resistance was insufficient at any addition amount. In Comparative Example 9 in which the addition amount of the flame retardant is less than the specified value, the flame retardancy is insufficient, and in Comparative Example 10 in which the amount of the flame retardant is greater than the specified value, the elongation is insufficient.

DESCRIPTION OF SYMBOLS 1 Copper conductor 2 Insulator 3 Sheath 4 Interposition 5 Holding winding tape

Claims (6)

10 to 30 parts by mass of polypropylene; 4 to 10 parts by mass of ethylene, α-olefin having a polar group and maleic anhydride 4 to 10 parts by mass; and 54 to 86 parts by mass of polyolefin resin other than polypropylene, total 100 parts by mass A polymer consisting of
A halogen-free flame retardant resin composition comprising 180 to 250 parts by mass of a halogen-free flame retardant. The non-halogen hard flame according to claim 1, which has a hardness of 50 to 60 as type D durometer hardness, and has a volume resistivity of 1.0 × 10 ¹⁰ Ω · cm or more after being immersed in hot water at 80 ° C. for 30 days. A flammable resin composition.   The non-halogen flame retardant resin composition according to claim 1 or 2, wherein the polyolefin resin is an ethylene / vinyl acetate copolymer having a vinyl acetate content (VA amount) of 20 to 45%.   The non-halogen flame retardant resin composition according to any one of claims 1 to 3, wherein the terpolymer is a terpolymer of ethylene, ethyl acrylate, and maleic anhydride. Conductors,
The electric wire provided with the insulator coat | covered and formed in the outer periphery of the said conductor using the non-halogen flame-retardant resin composition of any one of Claims 1-4. A conductor and an outer periphery of the conductor each provided with an insulator formed and formed, and a plurality of wires twisted together,
A holding member wound around an outer periphery of the plurality of twisted electric wires;
The cable provided with the sheath coat | covered and formed in the outer periphery of the said pressing member using the halogen-free flame-retardant resin composition of any one of Claims 1-4.

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